The structure and physico-chemical properties of the Na-type organophobic layered alumosilicate montmorillonite mineral (sample B1) and its three orgamoclays (B2, B3, B4) have been investigated in this work. Polyatomic ions of octadecylbenzyldimethylammonium chloride (OBDM), dioctadecyldimethylammonium chloride (DODM) and cetyltrimethylammonium bromide (CTAB) were used as surface modifiers for B2, B3, B4, correspondingly. X-ray diffraction method allowed to determine interlayer distances for these samples, and also the sizes of ‘galleries’, i.e. the studies of the small angle scattering gave the number of lamellae in the crystals of these clay minerals. The correlations between the structure formation and optical properties of the nematic liquid crystal – organoclay composites have been found out. The differences of these properties are shown to be mainly caused by the chemical nature of the modifier, being a crucial factor for the character of interactions on the organic matrix – inorganic particle boundary.